Mechanisms of hydrogen cyanide formation from the pyrolysis of amino acids and related compounds

Johnson, William R.; Kang, John C.

doi:10.1021/jo00800a038

Cited by 73 publications

(42 citation statements)

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“…The resulting H 2 N-Å CH 2 radical can undergo a one-electron oxidation to HC 2 @NH [27], a molecule that is also an intermediate in HCN production by pyrolysis of glycine and other amino acids [28]:…”

Section: A Plausible Radical-based Mechanism For the Syntheses Of Co mentioning

confidence: 99%

A glycyl free radical as the precursor in the synthesis of carbon monoxide and cyanide by the [FeFe]‐hydrogenase maturase HydG

Nicolet¹,

Martin²,

Tron³

et al. 2010

FEBS Letters

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Section: A Plausible Radical-based Mechanism For the Syntheses Of Co mentioning

confidence: 99%

A glycyl free radical as the precursor in the synthesis of carbon monoxide and cyanide by the [FeFe]‐hydrogenase maturase HydG

Nicolet¹,

Martin²,

Tron³

et al. 2010

FEBS Letters

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“…BB is considered to be the major source of HCN in the atmosphere (Li et al, , 2009Liang et al, 2007;Shim et al, 2007) via the pyrolysis of N-containing species within the fuel (Johnson and Kang, 1971;Glarborg et al, 2003). Cooking fire emissions of HCN have also been observed in Mexico and Africa (Christian et al, 2010), although concentrations fell below Fourier transform IR (FTIR) detection limits.…”

Section: Introductionmentioning

confidence: 99%

Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

et al. 2013

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A chemical ionisation mass spectrometer (CIMS) was developed for measuring hydrogen cyanide (HCN) from biomass burning events in Canada using I⁻ reagent ions on board the FAAM BAe-146 research aircraft during the BORTAS campaign in 2011. The ionisation scheme enabled highly sensitive measurements at 1 Hz frequency through biomass burning plumes in the troposphere.

A strong correlation between the HCN, carbon monoxide (CO) and acetonitrile (CH₃CN) was observed, indicating the potential of HCN as a biomass burning (BB) marker. A plume was defined as being 6 standard deviations above background for the flights. This method was compared with a number of alternative plume-defining techniques employing CO and CH₃CN measurements. The 6-sigma technique produced the highest R² values for correlations with CO. A normalised excess mixing ratio (NEMR) of 3.68 ± 0.149 pptv ppbv⁻¹ was calculated, which is within the range quoted in previous research (Hornbrook et al., 2011). The global tropospheric model STOCHEM-CRI incorporated both the observed ratio and extreme ratios derived from other studies to generate global emission totals of HCN via biomass burning. Using the ratio derived from this work, the emission total for HCN from BB was 0.92 Tg (N) yr⁻¹

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“…Pyrolysis of nitrogen atom (N)-containing functionalities in the fuel is the primary mechanism proposed for HCN release from biomass combustion (Johnson and Kang, 1971;Glarborg et al, 2003). Hydrogen cyanide has been measured from field biomass fires (Hurst et al, 1994a, b;Goode et al, 2000;Yokelson et al, 2007;Crounse et al, 2009), and from laboratory biomass combustion systems (Lobert et al, 1991;Holzinger et al, 1999;Christian et al, 2004;Becidan et al, 2007).…”

Section: Introductionmentioning

confidence: 99%

A gas chromatographic instrument for measurement of hydrogen cyanide in the lower atmosphere

et al. 2012

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Abstract. A gas-chromatographic (GC) instrument was developed for measuring hydrogen cyanide (HCN) in the lower atmosphere. The main features of the instrument are (1) a cryogen-free cooler for sample dehumidification and enrichment, (2) a porous polymer PLOT column for analyte separation, (3) a flame thermionic detector (FTD) for sensitive and selective detection, and (4) a dynamic dilution system for calibration. We deployed the instrument for a ∼4 month period from January-June, 2010 at the AIRMAP atmospheric monitoring station Thompson Farm 2 (THF2) in rural Durham, NH. A subset of measurements made during 3-31 March is presented here with a detailed description of the instrument features and performance characteristics. The temporal resolution of the measurements was ∼20 min, with a 75 s sample capture time. The 1σ measurement precision was <10 % and the instrument response linearity was excellent on a calibration scale of 0.10-0.75 ppbv (±5 %). The estimated method detection limit (MDL) and accuracy were 0.021 ppbv and 15 %, respectively. From 3-31 March 2010, ambient HCN mixing ratios ranged from 0.15-1.0 ppbv (±15 %), with a mean value of 0.36 ± 0.16 ppbv (1σ ). The approximate mean background HCN mixing ratio of 0.20 ± 0.04 ppbv appeared to agree well with tropospheric column measurements reported previously. The GC-FTD HCN measurements were strongly correlated with acetonitrile (CH 3 CN) measured concurrently with a proton transfer-reaction mass spectrometer (PTR-MS), as anticipated given our understanding that the nitriles share a common primary biomass burning source to the global atmosphere. The nitriles were overall only weakly correlated with carbon monoxide (CO), which is reasonable considering the greater diversity of sources for CO. However, strong correlations with CO were observed on several nights under stable atmospheric conditions and suggest regional combustion-based sources for the nitriles. These results demonstrate that the GC-FTD instrument is capable of making long term, in-situ measurements of HCN in the lower atmosphere. To date, similar measurements have not been performed, yet they are critically needed to (1) better evaluate the regional scale distribution of HCN in the atmosphere and (2) discern the influence of biomass burning on surface air composition in remote regions.

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Mechanisms of hydrogen cyanide formation from the pyrolysis of amino acids and related compounds

Cited by 73 publications

References 0 publications

A glycyl free radical as the precursor in the synthesis of carbon monoxide and cyanide by the [FeFe]‐hydrogenase maturase HydG

A glycyl free radical as the precursor in the synthesis of carbon monoxide and cyanide by the [FeFe]‐hydrogenase maturase HydG

Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires

A gas chromatographic instrument for measurement of hydrogen cyanide in the lower atmosphere

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